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US9261718B2 - Composite thin film and composite nanocrystals containing europium (II) compound and metal - Google Patents

Composite thin film and composite nanocrystals containing europium (II) compound and metal Download PDF

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US9261718B2
US9261718B2 US14/002,876 US201214002876A US9261718B2 US 9261718 B2 US9261718 B2 US 9261718B2 US 201214002876 A US201214002876 A US 201214002876A US 9261718 B2 US9261718 B2 US 9261718B2
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thin film
composite
metal
nanoparticle
compound
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US20140055855A1 (en
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Yasuchika Hasegawa
Akira Kawashima
Mina Kumagai
Koji Fushimi
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Hokkaido University NUC
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/09—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on magneto-optical elements, e.g. exhibiting Faraday effect
    • G02F1/093—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on magneto-optical elements, e.g. exhibiting Faraday effect used as non-reciprocal devices, e.g. optical isolators, circulators
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
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    • C01F17/224—Oxides or hydroxides of lanthanides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/0009—Materials therefor
    • G02F1/0036—Magneto-optical materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/09—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on magneto-optical elements, e.g. exhibiting Faraday effect
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B11/00—Recording on or reproducing from the same record carrier wherein for these two operations the methods are covered by different main groups of groups G11B3/00 - G11B7/00 or by different subgroups of group G11B9/00; Record carriers therefor
    • G11B11/10—Recording on or reproducing from the same record carrier wherein for these two operations the methods are covered by different main groups of groups G11B3/00 - G11B7/00 or by different subgroups of group G11B9/00; Record carriers therefor using recording by magnetic means or other means for magnetisation or demagnetisation of a record carrier, e.g. light induced spin magnetisation; Demagnetisation by thermal or stress means in the presence or not of an orienting magnetic field
    • G11B11/105—Recording on or reproducing from the same record carrier wherein for these two operations the methods are covered by different main groups of groups G11B3/00 - G11B7/00 or by different subgroups of group G11B9/00; Record carriers therefor using recording by magnetic means or other means for magnetisation or demagnetisation of a record carrier, e.g. light induced spin magnetisation; Demagnetisation by thermal or stress means in the presence or not of an orienting magnetic field using a beam of light or a magnetic field for recording by change of magnetisation and a beam of light for reproducing, i.e. magneto-optical, e.g. light-induced thermomagnetic recording, spin magnetisation recording, Kerr or Faraday effect reproducing
    • G11B11/10582—Record carriers characterised by the selection of the material or by the structure or form
    • G11B11/10586—Record carriers characterised by the selection of the material or by the structure or form characterised by the selection of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y99/00—Subject matter not provided for in other groups of this subclass
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/38—Particle morphology extending in three dimensions cube-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • Various aspects and embodiments of the present invention relate to composite nanocrystals and a composite thin film containing an Eu (II) compound and a metal.
  • Patent Document 1 a Bi-substituted garnet is known (for example, see Patent Document 1).
  • composite film is produced by containing nanoparticles of Au, Al, Ag or the like within Bi-substituted garnet thin film, thus electric polarization induced by the metal nanoparticles is increased by surface plasmon resonance of the metal nanoparticles, and thereby magnetooptic effects of the Bi-substituted garnet are increased.
  • An object of the present invention is to provide a material having an improved magnetooptical property.
  • the Faraday effect of the Eu (II) compound is considerably increased by arranging the Eu (II) compound close to a metal which generates a localized electric field on its surface by light irradiation.
  • the composite nanocrystal related to one aspect of the present invention is produced by a composite with an Eu (II) compound nanoparticle and a metal nanoparticle.
  • Such production generates quantum size effects of the Eu (II) compound nanoparticle, while the surface plasmon of the metal nanoparticle can be used.
  • the magnetooptical property can be improved.
  • the Eu (II) compound nanoparticle may be made of a material selected from EuO, EuS, EuSe or EuTe.
  • the metal nanoparticle may be made of a metal material selected from Ag, Au, Pt and Cu, a combination of the metal materials, or an alloy of two or more selected from Ag, Au, Pt and Cu.
  • the crystalline Eu (II) compound nanoparticle is combined with the crystalline metal nanoparticle through a compound having the same or different two or more of a thiol group, a hydroxyl group, a carboxyl group, a sulfonic group, a cyano group, an amino group or a pyridyl group.
  • a composite thin film related to another aspect of the present invention is produced by the composite with the Eu (II) compound nanoparticle and the metal nanoparticle.
  • the thus constituted composite thin film generates the same actions and effects as the aforementioned composite nanocrystal.
  • a magnetooptical material related to another aspect of the present invention is produced by using the composite nanocrystal or the composite thin film. Since the Eu (II) compound nanoparticle has a feature of change in magnetic susceptibility by light irradiation, for example, adoption of the composite nanocrystal or the composite thin film for a Faraday rotator allows for provision of an optical device impractical in conventional technologies like an optical isolator in which a polarization plane can be rotated corresponding to light.
  • an inorganic glass or polymeric thin film related to another aspect of the present invention is produced by using the composite nanocrystal or the composite thin film.
  • a magnetooptical material such as a novel optical isolator and a recording medium can be provided.
  • an optical isolator related to another aspect of the present invention is equipped with a Faraday rotator produced by using the composite nanocrystal, the composite thin film, the magnetooptical material or the inorganic glass thin film.
  • a Faraday rotator produced by using the composite nanocrystal, the composite thin film, the magnetooptical material or the inorganic glass thin film.
  • a manufacturing method of composite nanocrystal related to another aspect of the present invention comprises a step of synthesizing a crystalline Eu (II) compound nanoparticle by thermal reduction of a complex containing Eu (III), a step of synthesizing a crystalline metal nanoparticle by thermal reduction of a complex containing a metal, and a step of synthesizing a composite nanocrystal by combining the Eu (II) compound nanoparticle with the metal nanoparticle through a compound having the same or different two or more of a thiol group, a hydroxyl group, a carboxyl group, a sulfonic group, a cyano group, an amino group or a pyridyl group.
  • the composite nanocrystal After the crystalline Eu (II) compound nanoparticle and the crystalline metal particle are individually made, they are combined through the compound having the same or different two or more of a thiol group, a hydroxyl group, a carboxyl group, a sulfonic group, a cyano group, an amino group or a pyridyl group, thereby the composite nanocrystals can be synthesized.
  • a manufacturing method of composite nanocrystal related to another aspect of the present invention comprises a step of mixing a complex containing Eu (III) with a complex containing a metal, and a step of synthesizing a composite nanocrystal by thermal reduction of the mixed complex.
  • the composite nanocrystal can be synthesized by mixing the complex containing Eu (III) with the complex containing a metal concomitantly with thermal reduction.
  • a manufacturing method of a composite thin film related to another aspect of the present invention is a manufacturing method for electrochemically manufacturing the composite thin film, and comprises a step of dispersing the complex containing Eu (III) and the complex containing a metal in a solvent, and a step of applying a voltage by inserting a transparent electrode as a work electrode into the solvent to produce the composite thin film composed of the Eu compound nanoparticle and the metal nanoparticle on the transparent electrode.
  • the composite thin film can be produced by electrochemical actions.
  • a manufacturing method of a composite thin film related to another aspect of the present invention is a manufacturing method for electrochemically manufacturing the composite thin film, and comprises an Eu-dispersing step of dispersing the complex containing Eu (III) in a solvent, a metal-dispersing step of dispersing the complex containing a metal in the solvent, and a thin film-producing step of applying a voltage by inserting a transparent electrode as a work electrode into the solvent to produce the thin film composed of the Eu (II) compound or the metal on the transparent electrode, wherein the Eu-dispersing step, the thin film-producing step, the metal-dispersing step and the thin film-producing step are carried out in turn, alternatively the metal-dispersing step, the thin film-producing step, the Eu-dispersing step and the thin film-producing step are carried out in turn.
  • a layer structure composed of Eu (II) compound thin film and the metal thin film can be produced.
  • FIG. 1 represents a schematic view illustrating a manufacturing step of the EuS nanocrystalline particle.
  • FIG. 2 represents an MD pattern of the EuS nanocrystalline particle.
  • FIG. 3 represents a schematic view illustrating a manufacturing step of the Au nanocrystalline particle.
  • FIG. 4 represents a schematic view illustrating the EuS—Au composite nanocrystalline particle.
  • FIG. 5 represents a TEM image of the EuS—Au composite nanocrystal.
  • FIG. 6 represents a TEM image of the EuS—Au composite nanocrystal.
  • FIG. 7 represents an absorption spectrum of the EuS—Au composite nanocrystal.
  • FIG. 8 (A) represents an absorption spectrum of the EuS nanocrystal, and (B) represents an absorption spectrum of the EuS—Au composite nanocrystal.
  • FIG. 9 represents a schematic view illustrating a manufacturing equipment of the EuS/Au composite thin film.
  • FIG. 10 represents a cross-sectional SEM image of the EuS thin film.
  • FIG. 11 represents an SEM image of the EuS thin film.
  • FIG. 12 represents current-voltage properties of the EuS thin film.
  • FIG. 13 represents SEM images of each EuS thin film produced under different voltages applied.
  • (A) is at ⁇ 0.8 V
  • (B) is at ⁇ 1.2 V
  • (C) is at ⁇ 1.4 V
  • (D) is at ⁇ 1.7 V
  • (E) is at ⁇ 2.0 V.
  • FIG. 14 represents SEM images of the EuS thin film (applied voltage is ⁇ 1.2 V).
  • (A) to (D) represent results of observations at different scales respectively.
  • FIG. 15 represents results of EDS mappings of the EuS thin film (applied voltage is ⁇ 1.2 V).
  • A represents an SEM image
  • B represents a result of mapping of Eu
  • C represents a result of mapping of S
  • D represents a result of mapping of Si.
  • FIG. 16 represents a time change in a current value of the EuS thin film (applied voltage is ⁇ 1.2 V).
  • FIG. 17 represents measured results of photoabsorption spectra in example and comparative example.
  • FIG. 18 represents a schematic configuration of a conventional optical isolator.
  • FIG. 19 represents a schematic configuration of an optical isolator having a constitution that a polarization plane of a Faraday rotator is rotated by a laser light.
  • FIG. 20 represents Verdet constant spectrographies of a PMMA film containing the EuS crystal and a PMMA, film containing the composite nanocrystal.
  • the composite nanocrystal related to the embodiment of the present invention is a composite nanocrystal being a composite with a crystalline Eu (II) compound nanoparticle and a crystalline metal nanoparticle.
  • the composite nanocrystal means a nanosized composite crystal.
  • An average particle size of the Eu (II) compound nanoparticle is, for example, about 5 nm to 100 nm.
  • an europium chalcogenide of, for example, EuO, EuS, EuSe or EuTe is used as a material of the Eu (II) compound nanoparticle.
  • An average particle size of the metal nanoparticle is, for example, about 5 nm to 100 nm.
  • a material of the metal nanoparticle may be any metal material which generates a localized electric field on its surface by light irradiation, and for example, Ag, Au, Pt, Cu or their combination is used. Alternatively, an alloy of two or more selected from Ag, Au, Pt and Cu may be used.
  • the composite nanocrystal is constituted so that interfaces of the crystalline Eu (II) compound nanoparticle and the crystalline metal nanoparticle are joined.
  • any means for joining the interfaces may be employed, for example, the Eu (II) compound nanoparticle and the metal nanoparticle may be simultaneously crystallized and synthesized, and thereby joined so that each particle adhered to each other, alternatively the crystalline Eu (II) compound nanoparticle and the crystalline metal nanoparticle may be separately produced and joined through a joint material.
  • a compound having the same or different two or more of a thiol group, a hydroxyl group, a carboxyl group, a sulfonic group, a cyano group, an amino group or a pyridyl group is used.
  • a compound having two or more thiol groups for example, ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,2-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 3,6-dioxaoctane-1,8-dithiol, 2,2-oxydiethanethiol, 2,3-dimercapto-1-propanol, dithioerythritol, dithiothreitol, 1,4-benzenedithiol, 1,3-benzenedithiol, 1,2-benzenedithiol, 4-chloro-1,3-benzenedithiol, 4-methyl-1,2-benzenedithiol, 4,5-d
  • a compound having a thiol group and a hydroxyl group for example, 1-mercaptoethanol, 2-mercaptoethanol, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mere aptoethyl-2-methyl-1,3-propanediol, 2-methylcaptoethyl-2-ethyl-1,3-propanediol or the like is used.
  • a compound having a thiol group and a carboxyl group for example, thioglycolic acid, thiomalic acid, thiosalicyclic acid, mercaptopropionic acid or the like is used.
  • a compound having a thiol group and a sulfonic group for example, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 2-mercaptobenzenesulfonic acid, 3-mercaptobenzenesulfonic acid, 4-mercaptobenzenesulfonic acid or the like is used.
  • a compound having a thiol group and a cyano group for example, 2-cyanobenzenethiol or the like is used.
  • a compound having a thiol group and an amino group for example, aminothiophenol, aminotriazolethiol or the like is used.
  • a compound having a thiol group and a pyridyl group for example, pyridinethiol or the like is used.
  • the composite nanocrystal When the composite nanocrystal is irradiated with light, plasmon is generated on the surface of the metal particle to cause the electric field enhancing effect.
  • This electric field enhancement affects magnetooptical properties of the Eu (II) compound nanoparticle combined with the metal particle.
  • the magnetooptic effects of the Eu (II) compound nanoparticle itself can be increased.
  • the Eu (II) compound is used as a nanoparticle, thereby the Faraday effect can be shown across a wide region from ultraviolet to infrared regions at room temperature due to the quantum size effect.
  • the compound can be used as an optical element or the like corresponding to a wide range of wavelengths.
  • an Eu (III) carbamide complex as a synthetic raw material of the EuS nanocrystal: [Eu(PPh 4 )(S 2 CNEt 2 )] and an Au complex as a synthetic raw material of the Au nanocrystal: [Au(PPh 3 )Cl] are prepared.
  • the Eu (III) carbamide complex and the Au complex are dispersed in a solvent.
  • a solvent for example, oleylamine is used.
  • An amount of oleylamine is, for example, about 4.5 g.
  • the resulting solution is heated under a nitrogen atmosphere.
  • heating is conducted, for example, at 140° C. for 5 minutes. Thereby a black solution can be obtained.
  • it is further heated at a high temperature under a nitrogen atmosphere.
  • heating is conducted, for example, at 180° C. for 10 minutes. Thereby, an aubergine solution can be obtained.
  • the resulting solution is centrifuged.
  • centrifugation is conducted, for example, at 7000 rpm, at room temperature for 5 minutes, and oleylamine is used as a solvent. Thereby, an aggregate can be obtained. Subsequently, the resulting aggregate is further centrifuged. As a condition, centrifugation is conducted, for example, at 7000 rpm, at room temperature for 5 minutes, and chloroform is used as a solvent. Thereby, an EuS/Au composite nanocrystal can be obtained.
  • the second manufacturing method of the composite nanocrystal related to the embodiment will be explained with reference to FIG. 1-6 . Similar to the first manufacturing method, a case where EuS is used as an Eu (II) compound and Au is used as a metal will be explained.
  • an Eu (III) carbamide complex as a synthetic raw material of the EuS nanocrystal: [Eu(PPE 4 )(S 2 CNEt 2 )] and an Au complex as a synthetic raw material of the Au nanocrystal: [Au(PPh 3 )Cl] are prepared.
  • the EuS nanocrystalline particle and the Au nanocrystalline particle are individually synthesized.
  • a solution in which an Eu (III) carbamide complex is dispersed in a solvent is prepared and heated.
  • the solvent for example, oleylamine is used.
  • heating is conducted, for example, at 140° C. for 10 minutes.
  • the resulting solution is heated under a nitrogen atmosphere.
  • heating is conducted, for example, at 300° C. for 6 hours.
  • FIG. 2 Structural evaluation of the EuS nanocrystalline particle obtained in the aforementioned process is shown in FIG. 2 .
  • the EuS nanocrystalline particle may be produced by, for example, a method using a reduction reaction of Eu (III) through light described in Japanese Patent Application Laid-Open No. 2001-354417.
  • the EuO crystal or the EuS crystal is generated by dissolving, for example, europium nitrate and urea in methanol and irradiating this with ultraviolet light.
  • FIG. 3 a solution in which an Au complex is dispersed in a solvent is prepared and heated.
  • the Au nanocrystalline particle can be obtained by thermal reduction.
  • the EuS nanocrystalline particle is combined with the Au nanocrystalline particle.
  • a joint material for example 1,6-hexanedithiol is used.
  • the EuS nanocrystalline particle is combined with the Au nanocrystalline particle, resulting in an EuS—Au composite nanocrystalline particle.
  • FIGS. 5 and 6 are TEM images. As shown in FIGS. 5 and 6 , Au having a particle size of about 10 nm was confirmed to be combined with EuS having a particle size of about 15 nm.
  • FIG. 7 represents an absorption spectrum at a wavelength ranging 400 nm to 900 nm. As shown in FIG. 7 , a 4 f - 5 d band and a plasmon absorption band of the EuS—Au composite nanocrystalline particle was confirmed. In addition, (A) in FIG.
  • the composite thin film related to the embodiment of the present invention is a composite thin film composed of the crystalline Eu (II) compound nanoparticle and the crystalline metal nanoparticle.
  • a film thickness is, for example, about 5 nm to 100 ⁇ m.
  • An average particle size of the Eu (II) compound nanoparticle is, for example, about 5 nm to 100 nm.
  • an europium chalcogenide of, for example, EuO, EuS, EuSe or EuTe is used as a material of the Eu (II) compound nanoparticle.
  • An average particle size of the metal nanoparticle is, for example, about 5 nm to 100 nm.
  • a material of the metal nanoparticle may be any metal which generates a localized electric field on its surface by light irradiation, and for example, Ag, Au, Pt, Cu or their combination is used. Alternatively, an alloy of two or more selected from Ag, Au, Pt and Cu may be used.
  • the composite thin film is constituted so that interfaces of the crystalline Eu (II) compound nanoparticle and the crystalline metal nanoparticle are joined.
  • any means for joining the interfaces may be employed, for example, the Eu (II) compound nanoparticle and the metal nanoparticle may be simultaneously crystallized and deposited, and thereby joined, alternatively the thin film comprising the metal nanoparticle may be laminated onto the thin film comprising the Eu (II) compound nanoparticle, alternatively the metal nanoparticle may be doped to the thin film comprising the Eu (II) compound nanoparticle.
  • the aforementioned composite thin film When the aforementioned composite thin film is irradiated with light, plasmon is generated on the surface of the metal particle to cause the electric field enhancing effect.
  • This electric field enhancement affects magnetooptical properties of the Eu (II) compound nanoparticle combined with the metal particle.
  • the magnetooptic effects of the Eu (II) compound nanoparticle itself can be increased.
  • the Eu (II) compound is used as a nanoparticle, thereby the Faraday effect can be shown across a wide region from ultraviolet to infrared at room temperature due to the quantum size effect.
  • the compound can be used as an optical element or the like corresponding to a wide range of wavelengths.
  • an Eu (III) carbamide complex as a synthetic raw material of the EuS nanocrystal: [Eu(PPh 4 )(S 2 CNEt 2 )] and an Au complex as a synthetic raw material of the Au nanocrystal: [Au(PPh3)Cl] are prepared.
  • Components of the complex are identified by NMR, IR, elementary analysis or the like.
  • the Eu (III) carbamide complex, the Au complex and a supporting electrolyte are dispersed in a solvent.
  • a solvent for example, acetonitrile is used.
  • the Eu (III) carbamide complex and the Au complex may be individually dispersed in different solvents.
  • a transparent electrode is used as a work electrode WE for electrochemical synthesis of the thin film, and the transparent electrode WE, a reference electrode RE and a counter electrode CE are inserted into the solvent, to which a voltage is applied during degasification by Ar, as shown in FIG. 9 .
  • an indium tin oxide (ITO) is used as the transparent electrode
  • platinum (Pt) is used for the reference electrode and the counter electrode.
  • the transparent electrode When the Eu (III) carbamide complex and the Au complex are dispersed in the solvent, the transparent electrode is inserted into the solvent, to which a voltage is applied, resulting in production of a composite thin film comprising the EuS nanoparticle and the Au nanoparticle on the transparent electrode.
  • the composite thin film can be electrochemically manufactured.
  • the transparent electrode is inserted into the solvent in which the Eu (III) carbamide complex is dispersed, to which a voltage is applied, resulting in production of an EuS thin film comprising the EuS nanoparticle on the transparent electrode.
  • the transparent electrode is inserted into the solvent in which the Au complex is dispersed, to which a voltage is applied, resulting in production of an Au thin film comprising the Au nanoparticle on the EuS thin film.
  • Production steps of the Au thin film and the EuS thin film may be alternately carried out. Thereby, a layer structure of the EuS/Au composite thin film is produced.
  • FIGS. 10 and 11 are images by a scanning electron microscope (SEM). As shown in FIG. 10 , a thin film of about 100 ⁇ m was confirmed to be produced on the transparent electrode. In addition, as shown in FIG. 11 , the thin film was confirmed to be composed of a nanoparticle. Furthermore, elemental constituents were evaluated by an energy dispersion spectroscopy (EDS). As a result, a ratio of Eu:S was confirmed to be 1:1.
  • SEM scanning electron microscope
  • the voltage applied to the reference electrode and the counter electrode was changed at 100 mV/s, and current-voltage characteristics at applied voltages ranging 0-2 V were determined, in order to verify whether Eu (III) changed into Eu (II) under the aforementioned condition.
  • the result is shown in FIG. 12 .
  • the horizontal axis represents voltage
  • the vertical axis represents current.
  • the measurement result of the case where the solvent contains no sample is represented by a dashed line (Blank), and the measurement result of the case where the solvent contains the sample is represented by a continuous line (Eu complex).
  • EuS thin films of sample No. 1 to sample No. 5 were produced using the equipment shown in FIG. 9 in order to verify a constant voltage suitable for application to the reference electrode and the counter electrode.
  • the applied voltage at the time of production of sample No. 1 was ⁇ 0.8 V
  • the applied voltage at the time of production of sample No. 2 was ⁇ 1.2 V
  • the applied voltage at the time of production of sample No. 3 was ⁇ 1.4 V
  • the applied voltage at the time of production of sample No. 4 was ⁇ 1.7 V
  • the applied voltage at the time of production of sample No. 5 was ⁇ 2.0 V.
  • the application time of the voltage was 3 hours. Surface structures of the obtained sample No. 1 to sample No. 5 were observed.
  • FIG. 13 represents SEM images of the EuS thin film.
  • (A) is an SEM image of sample No. 1
  • (B) is an SEM image of sample No. 2
  • (C) is an SEM image of sample No. 3
  • (D) is an SEM image of sample No. 4
  • (E) is an SEM image of sample No. 5.
  • FIG. 13 (A) it was confirmed that, in the case of the applied voltage of ⁇ 0.8 V, a film was not formed but an island structure was formed. This is due to insufficient growth of EuS caused by insufficient current.
  • (C) to (E) in FIG. 13 it was confirmed that, in the case of the applied voltage of ⁇ 1.4 V or higher, a part of the film was stripped, resulting in a discontinuous film.
  • FIG. 14 represents SEM images of the EuS thin film of sample No. 2.
  • the scales of the SEM images (A), (B), (C) and (D) are in ascending order, and observation in ⁇ m unit was conducted in detail.
  • FIG. 14 when the applied voltage was ⁇ 1.2 V, production of a thin film was confirmed.
  • components of sample No. 2 were measured.
  • sample No. 2 an area where a part of the continuous film was stripped was found to measure it, and additionally a glass substrate coated with ITO was measured.
  • FIG. 15 represents results of EDS mapping of sample No. 2.
  • (A) represents an SEM image
  • (B) represents a result of mapping of Eu
  • (C) represents a result of mapping of S
  • (D) represents a result of mapping of Si.
  • white blanks represent areas detected as elements. As shown in FIG. 15 , it was confirmed that the ratio of Eu and S was 1:1 in areas other than Si, that is, areas where films were produced.
  • FIG. 16 represents a time change in a current value at the time of production of sample No. 2.
  • the horizontal axis represents time, and the vertical axis represents the current value.
  • the current value became constant by applying a constant voltage ( ⁇ 1.2 V) for a long time in electrochemical synthesis. For example, after 4 ⁇ 10 3 [s], the current value became nearly constant.
  • the fact that the current value becomes constant means steady reaction, that is, the fact that the same reactions constantly occur at the same speed. In other words, it was confirmed that, first, EuS accumulated on the surface of ITO, and the film thickness grew with time, then only reaction for accumulating EuS on EuS constantly occurred at the same speed.
  • FIG. 17 represents measured results of photoabsorption spectra of sample No. 2 deposited on ITO on the glass substrate and the glass substrate coated with ITO.
  • the horizontal axis represents wavelength, and the vertical axis represents intensity.
  • the photoabsorption spectrum of the glass substrate coated with ITO is represented by a dashed line, and photoabsorption spectrum of sample No. 2 is represented by a continuous line.
  • absorption of light was confirmed. That is, presence of Eu (II) was confirmed.
  • FIG. 18 represents a schematic configuration of a conventional optical isolator. As shown in FIG. 18 , in the structure of the optical isolator, a Faraday rotator 10 is placed between a polarizer 11 and an analyzer 12 , and the Faraday rotator 10 is sandwiched between permanent magnets 13 applying a magnetic field.
  • forward light introduced from an optical fiber 14 a is linearly-polarized by a polarizer 11 , then light with a polarization plane rotated by the Faraday rotator 10 is introduced to an optical fiber 14 b through the analyzer 12 .
  • backward light (optical feedback) is linearly-polarized by the analyzer 12 , and its polarization plane is rotated by the Faraday rotator 10 , but the polarization plane of light after rotation is in discord with the polarizer 11 , thus light cannot pass through the polarizer 11 , and the optical feedback is blocked there.
  • the Faraday rotator 10 one made from garnet crystal or the like has been conventionally used.
  • the Faraday rotator 10 is produced by using the composite nanocrystal or the composite thin film containing the Eu (II) compound, the same polarization rotation effect as the garnet crystal Faraday rotator 10 can be obtained. Hence, a household optical isolator for short-haul communication can be produced at a low price.
  • optical isolators now on the market correspond to only the near infrared region
  • the optical isolator equipped with the Faraday rotator 10 produced by using the aforementioned composite nanocrystal or composite thin film containing the Eu (II) compound corresponds to ultraviolet region as well as the visible region, and can also be used if multiwavelength communication is realized in the near future.
  • the aforementioned composite nanocrystal or composite thin film containing the Eu (II) compound can be utilized for optical switch based on magnetooptic effects.
  • it can be adopted as a Faraday rotator of an optical switch.
  • the composite nanocrystal and the composite thin film containing the Eu (II) compound change in magnetic susceptibilities by light irradiation, they are expected to be applied to a device controllable with light.
  • the composite nanocrystal and the composite thin film containing the Eu (II) compound are adopted for the Faraday rotator 10 , and a light source such as a laser light source which can irradiate the Faraday rotator 10 is prepared, thereby the following two applications can be given.
  • the optical isolator 18 is constituted so that lights with two wavelengths are output from the optical fiber 14 a , and when light is not irradiated, the optical isolator with magnet is switched to an A-wavelength optical isolator, and when light is irradiated, the optical isolator with magnet is switched to a B-wavelength (for example. A+ ⁇ ) optical isolator.
  • A-wavelength optical isolator for example. A+ ⁇
  • FIG. 19 An optical isolator which allows the polarization plane to rotate in response to light without the permanent magnet in FIG. 18 can be made.
  • FIG. 19 One example of such an optical isolator is shown in FIG. 19 .
  • This photoresponsive isolator has almost the same structure as the conventional optical isolators, but has the following differences. That is, it has a laser light source 15 instead of a permanent magnet, and laser light emitted from a laser light source 15 enters into the Faraday rotator 10 by a dielectric mirror 16 , thereby the magnetic susceptibility of the Faraday rotator 10 is changed, so that the polarization plane is changed.
  • a thin film having a novel property can be produced by adding the aforementioned composite nanocrystal containing the Eu (II) compound to an inorganic glass thin film and a polymeric thin film.
  • a solution containing the composite nanocrystal is rendered a colloidal solution by hydrolysis and condensation polymerization, furthermore enhanced reaction produces a gel without fluidity, and this gel is heat-treated to produce an inorganic glass thin film containing the composite nanocrystal.
  • the polymeric thin film containing the composite nanocrystal can be produced, for example by dispersing the composite nanocrystal in a dissolved polymer, spraying it to a plate or the like and drying.
  • the aforementioned inorganic glass thin film and polymeric thin film may be utilized for various applications.
  • Kerr effect of the Eu (II) compound which rotates a polarization direction of a reflected light is utilized to produce a recording medium such as a magnetic optical disc writable and readable for data by using the composite nanocrystal containing the Eu (II) compound.
  • the magnetic optical disc while a magnetic field of which the strength does not so much as reverse the magnetization direction is applied on a recording surface made from a resin thin film containing the composite nanocrystal on the disc surface in an opposite direction of the magnetization direction, a temperature is raised by illuminating condensed laser light, so that the magnetization direction is reversed only in a part irradiated with the laser light, and data is written.
  • laser light weaker than the writing light is applied on the recording surface to detect difference in Kerr rotation angle of the reflected light by polar Kerr effects. That is, recorded signals can be read by detecting the difference in Kerr rotation angle as change in light intensity using a polarizer.
  • an optical device which cannot be realized under the conventional technology can be provided, for example, an optical isolator for two wavelengths can be composed of one optical isolator.
  • Verdet constant spectra were measured at room temperature. The measured results are shown in FIG. 20 .
  • the horizontal axis represents wavelength
  • the vertical axis represents a standardized Verdet constant [degOe ⁇ 1 abs ⁇ 1 ].
  • a rotation angle of a polarization plane is standardized by an applied magnetic field and an absorbency.
  • a great change of the Faraday rotation could be found at a wavelength region of the Au plasmon absorption band. That is, the Au plasmon was confirmed to affect the magnetooptical property of EuS.
  • the thin film of example was confirmed to generate two times Faraday effects as compared to that of the thin film of comparative example.

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